Synthesis of rodlike ruthenium(II) coordination polymers having metal-nitrogen and metal-carbon bonds in their main chains

Abstract

Well-defined coordination polymers are described whose main chains are held together by pseudo-octahedral ruthenium(II) complexes in which five ligands are nitrogen and one ligand is carbon. In the first step of polymer synthesis, the bis-tridentate ligand 4,4''-bis[4'-(2,2':6',2''-terpyridine)]-2',5'-dihexyl-p-terphenyl is treated with two equivalents of ruthenium(III) chloride. The resulting dinuclear metal-monomer is subsequently activated by exchanging the remaining three chloro ligands at each ruthenium center by acetone as a more easily substitutable ligand. The activated metal monomer is treated with equimolar amounts of 4,4''-bis[4'-(6'-phenyl-2,2'-bipyridine)]-2',5'-dihexyl-p-terphenyl as a bis-tridentate ligand monomer. During this conversion, rodlike chains grow through the formation of two further metal-nitrogen bonds and one carbon-nitrogen bond at every ruthenium center. The homogeneous constitution of the readily soluble polymers is proven, and their degrees of polycondensation are roughly estimated to be P n ≥ 20, using 1 H and 13 C NMR spectroscopy. UV-vis absorption spectra show the polymers to behave like chains of electronically independent metal complexes. Due to the carbon-ruthenium bond, however, λ max appears at a longer wavelength (approx. 530 nm) than in the related coordination compounds with only nitrogen-ruthenium bonds. There, λ max is around 500 nm.

New Functional Polymers and Materials Based on 2,2′:6′,2″‐Terpyridine Metal Complexes

“…7). [23] However, in this case a heteroleptic complexation was used, where one of the ligands does not consist of a terpyridine, but of a 2-phenyl-bipyridine. In this case, in addition to the five nitrogens, a carbanion completes the complexation to the ruthenium(II) center.…”

Protective effect of poly(4-Vinylpyridine) containing surface films to the corrosion of copper

“…2,3 Recently, the importance of developing macromolecular complexes was highlighted because of their optical, magnetic, electronic and solution properties. 4 For instance, the conducting and thermal properties of poly(4-vinylpyridine) (P4VP) are significantly changed when the polymer is complexed with copper ions. 5 The technological applications of the P4VP/ copper system include reactive blending, 6 catalyst, [7][8][9] cation exchange resins and membranes designed to preconcentrate metals from dilute solutions 10 or remove them from wastewater, 11 solid-state electrochemical cells, 12 circuit manufacturing on microscopic smoothly polymeric surfaces 13 and anti-corrosion methods.…”

Probing How Counterion Structure and Dynamics Determine Polyelectrolyte Solutions Using EPR Spectroscopy

“…Scheme 1 displays the structures of two rod-like, self-assembling coordination polymers with Ru 2? as the charge-bearing group along the chain (RuCP) [37,38]. The complex formation of Ru 2?…”

“…ions and two terpyridine-based spacer molecules leads to octahedrally coordinated Ru centers with kinetically stable coordination bonds (for details on synthesis see Refs. [37,38]). Several polymers of this kind with different organic spacer molecules and metal ions (especially of the Fe-group in the periodic table of elements) have recently been developed for two reasons.…”